TW200538563A

TW200538563A - High-purity Ru powder, sputtering target obtained by sintering the same, thin film obtained by sputtering the target and process for producing high-purity Ru powder

Info

Publication number: TW200538563A
Application number: TW094105011A
Authority: TW
Inventors: Yuichiro Shindo; Akira Hisano
Original assignee: Nikko Materials Co Ltd
Priority date: 2004-03-01
Filing date: 2005-02-21
Publication date: 2005-12-01
Also published as: KR20060120286A; CN1926252A; TWI303666B; US7578965B2; JP4522991B2; JP4907708B2; EP1724364A4; WO2005083136A1; EP1724364A1; KR100881851B1; JPWO2005083136A1; CN100552068C; EP1724364B1; JP2010047844A; US20070240992A1

Abstract

A high-purity Ru powder characterized in that the content of each of alkali metal elements, such as Na and K, is ≤ 10 wtppm while the content of Al is in the range of 1 to 50 wtppm. Further, there is provided a process for producing the high-purity Ru powder characterized in that electrolysis is carried out in a solution with the use of Ru raw material of ≤ 3N (99.9%) purity as an anode so as to effect purification thereof. Still further, there is provided a high-purity Ru powder for sputtering target production having its hazardous substance content minimized, which is less in the occurrence of particles at film formation, uniformalizing film thickness distribution, and which has a purity of ≥ 4N (99.99%), being suitable to formation of an electrode material for capacitor of semiconductor memory. Moreover, there are provided a sputtering target obtained by sintering the high-purity Ru powder; a thin film obtained by sputtering the target; and a process for producing the high-purity Ru powder.

Description

200538563 九、發明說明：【發明所屬之技術領域】本發明，係關於具有4N ( 99.99%)以卜料系电度之一種來成半導體記憶體之電容用電極材時較佳 ' 〜A趟革巴製造用离純度Ru粉末、由該高純度Ru粉末燒結成之濺鑛[以及由該靶濺鍍成之薄膜及高純度Ru粉末之製造方法。【先鈾技術】 ’現今，以於半導體電容之電極材料等用途正急速地擴。如此之電極，一般係以Ru靶濺鍍而形成。後所可靠性之半導體之動作性能，極力減低錢鍍 2料成之上述材料中對半導體元件有害之雜f係為重亦即，期盼能極力減少：200538563 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a capacitor electrode material having a capacity of 4N (99.99%) using semiconductor materials to form a semiconductor memory body. The manufacturing method of ion-purity Ru powder for bar manufacturing, sputter ore sintered from the high-purity Ru powder, and a method for producing a thin film sputtered from the target and a high-purity Ru powder. [Pre-Uranium Technology] ‘At present, applications such as electrode materials for semiconductor capacitors are rapidly expanding. Such electrodes are generally formed by sputtering a Ru target. The reliability of the operation performance of the semiconductors after the reliability is extremely low, and the impurities f that are harmful to the semiconductor elements in the above-mentioned materials made of metal plating are important. That is, I hope to reduce as much as possible:

Na、&等驗金屬元素、 _ u、Th等放射性元素、Na, & other metal elements, _u, Th and other radioactive elements,

Fe Ni、Co、Cr、Cu之過渡元素等元素，亚希望能具有4N即99.99% (重量）以上之純度。容^雜質係有害之理由，係因Na、K等驗金屬又元素，、乾絕緣Μ中移動，而成為m〇s_lsi界面特性變差之Fe, Ni, Co, Cr, Cu, and other transition elements, the element hopes to have a purity of 4N, that is, 99.99% (weight) or more. Impurities are the reason why impurities, such as Na, K, and other metal test elements, and dry insulation M move, and become the mOSS interface characteristics deteriorated.

力了、四，U、Th 楚》Μ I 备永 …生兀素，係由於該元素所放出之α線曰战為元件發生敕_ $Power, four, U, Th Chu "Μ I Bei Yong… Sheng Wusu, because of the alpha line released by this element, said that the war occurred for the element 敕 $

Fe、m、c〇孝錯拟S〇fte·)之原因；而所含雜質之接八# Cr Cl1之過渡元素等元素，則會成為界面接合部之不良狀況的原因。 5 200538563 其中’特別以Na、K等鹼金屬元素之有害性被指出。相反的，如 Fe、Ni、Γη ο 士# L〇、Cr、Cii之過渡元素等元素，則並不被視為那麼有害，而容許某種程度的存在。、核。寸以在之Ru革巴的組成，已揭示：驗金屬元素各未滿lppm、驗土類金屬元素各未滿—、過渡金屬元素各未，！刚^放射性元素各未滿1〇ppm、石炭及氣體成分元素 (氧氫氮氯）σ δ十未滿500ppm、氣體成份除外之舒之純度為99.995%以上，且A Q.々+斗 A1、Si各未滿ippm之釕（如，參照專利文獻1 );碳、氢、 ^ 、乳虱荨各兀*素之含量為iooPpm 以下、氣體成份除外之舒之站痒 1心4了之純度為99.995%以上（例如，參照專利文獻2 );鐵系元辛5 一京5ppm以下、驗金屬元素ippm、放射性元素0·0 lppm以下、破炎，鎢為lppm以下之釕（例如，參照專利文獻3 ) ; 9 9 · 9 9 9重量。/以μ今一更里/〇以上之高純度釕濺鍍 (例如，參照專利文獻4);驗金屬贩I屬兀素各〇1重量以下、鹼土類金屬元素各〇 ]舌曰里ppm -本々,壬旦、重置ppm以下、放射性同位素兀。 S _以下、氣體成分元素合計30重量以下\"·995厘重量％之高純度釕職錄乾（例如，參照專利文獻5) ’驗金屬、驗土類金屬、扣鐵、鎳、銅蓉久以下之高純度釕粉末（例如，參寻· PP-The reasons for Fe, m, and C0 are incorrect; and the elements such as the transition element of # CrCr1, which are impurities, will cause the poor condition of the interface junction. 5 200538563 Among them, ‘is particularly pointed out by the harmfulness of alkali metal elements such as Na and K. In contrast, elements such as Fe, Ni, Γη ο Shi # L0, Cr, and Cii transition elements are not considered to be so harmful, but are allowed to exist to some extent. , Nuclear. In terms of the composition of Ru Geba, it has been revealed that the test metal elements are each less than 1 ppm, the test soil metal elements are each less than, and the transition metal elements are each less! Each of the radioactive elements is less than 10 ppm, the charcoal and the gas component element (oxyhydrogen nitrogen chloride) σ δ is less than 500 ppm, and the purity of the compound except gas components is more than 99.995%, and A Q.々 + 斗 A1 Si is less than 1 ppm of ruthenium (for example, refer to Patent Document 1); the content of carbon, hydrogen, ^, and pectin * is less than 10oPpm, except for gas components. 99.995% or more (for example, refer to Patent Document 2); iron-based Yuanxin 5 to 5ppm or less, metal element ippm, radioactive element 0 · 1 lppm or less, rupture, tungsten is 1ppm or less ruthenium (for example, refer to Patent Document) 3); 9 9 · 9 9 9 weight. / Sputtered with high purity ruthenium above μ (for example, refer to Patent Document 4); each metal tester is 1% or less, and each alkaline earth metal element is 0. Benzoin, Rendan, below ppm, radioisotope. S _ or less, total gas component elements 30 weight or less \ " · 995% by weight of high-purity ruthenium job record (for example, refer to Patent Document 5) 'Metal inspection, soil inspection metals, iron deduction, nickel, copper hibiscus High-purity ruthenium powder under a long time

Ayr人 >丄c 亏〜又獻6) ; Na、K、Ayr people > 丄 c loss ~ 6 dedication; Na, K,

Ca、Mg合计5ppm以下、卜、Ni、r 〇·5〜50ppm、放射性同位素元素為5ppb以下為除去為99.999重量％以上之釕濺鍍 Y、Fe、Nl、Co (例如，表昭裒刹獻7) ; 99.999%以上之高純度 …、、專利文文獻8)。 “巴（例如，參照專利 6 200538563 專利文獻1 :日本特開平丨丨乃0163號公報專利文獻2 :日本特開2〇〇〇-34563號公報專利文獻3 :日本特開平丨1-217633號公報專利文獻4 :日本特開平9-4丨丨3丨號公報專利文獻5 :日本特開2〇〇2_1〇563 1號公報專利文獻6 :曰本特開平9-227966號公報專利文獻7 :日本特開平8-199350號公報專利文獻8 :曰本特開平8-301462號公報檢討上述專利文獻，則可說是揭示：為了保證半導體之動作性能，冑釕中所含被認為有害之雜質極力減低，而達到高純度化之釕之技術。然而，於半導體記憶體之電容用電極材形成時使用之濺鍍靶材，要求成膜時粒子產生少、膜厚分布均一之特性，但於現狀則有不足之問題。【發明内容】本發明，係提供-種極力減低有害物質、且粒子之產生少、成膜時之膜厚分布均—、並且具有4N( 99 99⑻ 以上純度之形成半導體記憶體之電容用電極材時較佳之°漉鍍靶製造用高純度Ru粉末、由該高純度Ru粉末燒結成：濺鍍靶、以及由該靶濺鍍成之薄膜及高純纟Ru :: 造方法。 & 本發明’係提供：1)一種高純度Ru粉末，其特徵在於， Na、K等鹼金屬元素之含量各$ 1〇卿-以下、…含量 7 200538563 為1〜5〇Wtppm; 2) 一種高純度Ru粉末，其特徵在於，ai 含量為5〜2〇wtppm; 3)如上述丨）或2)之高純度Ru粉末，其中，Fe、Nl、Co、Cr、Cu等過渡金屬元素之含量總計為lOOwtppm以下，u、Th等放射性元素之含量各為i〇wtppb 以下，4)如1)〜3)中任一項之高純度Ru粉末，不計氧、氮、氫等《成分’其純度為99·99%以上；5)如4)之高純度^ 粉末’其中，氧為l〇0wtppm以下；6)_種濺鍍靶及該靶濺鍍成之薄膜’其特徵在於’係自1}〜5)中任一項之高純度Ru粉末燒結而製成；7)—種高純度Ru粉末之製造方法，係製造㈣中任—項之高純度Ru粉末，其特徵在於，將純度3N (99.9%)以下之Ru原、料作為陽極，於溶液中進行電解以精製。 ^本發明，將靶製造原料之高純度Ru粉末中之Na、κ :鹼金屬元素之含量，控制成各為l〇wtPpm以下、且使其 3有Al 1〜5Gppm，藉此’可製造成膜時粒子之產生數少、Ca, Mg, total 5 ppm or less, Bu, Ni, r 0.5 to 50 ppm, radioisotope element 5 ppb or less, ruthenium sputtered Y, Fe, Nl, Co (excluding 99.999% by weight or more) 7); High purity above 99.999% ..., Patent Document 8). "For example, refer to Patent 6 200538563 Patent Document 1: Japanese Patent Application Laid-Open No. 0163 Patent Document 2: Japanese Patent Application Laid-Open No. 2000-34563 Patent Document 3: Japanese Patent Application Laid-Open No. 1-217633 Patent Document 4: Japanese Patent Application Laid-Open No. 9-4 丨丨 3 丨 Patent Document 5: Japanese Patent Application Laid-Open No. 0021-20063 Patent Literature 6: Japanese Patent Application Laid-Open No. 9-227966 Patent Literature 7: Japan Japanese Patent Application Laid-Open No. 8-199350 Patent Document 8: Japanese Patent Application Laid-Open No. 8-301462 reviews the above-mentioned patent documents, and it can be said that in order to ensure the operating performance of semiconductors, impurities considered to be harmful in ruthenium are extremely reduced. In order to achieve high-purity ruthenium technology. However, sputtering targets used in the formation of capacitor electrodes for semiconductor memories require characteristics such as small particle generation and uniform film thickness distribution during film formation, but in the current situation, [Problem of the invention] The present invention provides-a kind of highly effective reduction of harmful substances, with less particle generation, uniform film thickness distribution during film formation-and a formation half with a purity of 4N (99 99⑻ or more) The preferred electrode material for capacitors in body memory is a high-purity Ru powder for the production of ° 漉 plated targets. The high-purity Ru powder is sintered into: a sputtering target, and a thin film and high-purity 靶 Ru sputtered from the target: : Manufacturing method. &Amp; The present invention provides: 1) A high-purity Ru powder, characterized in that the content of alkali metal elements such as Na, K and the like are each $ 10- or less, and the content 7 200538563 is 1 ~ 5. Wtppm; 2) a high-purity Ru powder, characterized in that the ai content is 5 to 20 wtppm; 3) the high-purity Ru powder as described above 丨) or 2), wherein Fe, Nl, Co, Cr, Cu, etc. The total content of transition metal elements is 100wtppm or less, and the content of radioactive elements such as u and Th is each i0wtppb or less. 4) High-purity Ru powder such as any of 1) to 3), excluding oxygen, nitrogen, hydrogen, etc. "Composition 'its purity is 99.99% or more; 5) such as 4) high purity ^ powder', of which oxygen is 100wtppm or less; 6) _ a variety of sputtering targets and thin films sputtered by the target 'characteristics It is made by sintering a high-purity Ru powder according to any one of the following: 1) ~ 5); 7) —a method for producing a high-purity Ru powder, which is made of ㈣ The high-purity Ru powder of any one of the items is characterized in that a Ru raw material with a purity of 3N (99.9%) or less is used as an anode and electrolytically refined in a solution. ^ In the present invention, a high-purity Ru powder of a target manufacturing raw material is used. The content of Na and κ in the alkali metal elements is controlled to be 10 wtPpm or less, and 3 to 1 to 5 Gppm of Al, thereby 'the number of particles generated during film formation can be reduced,

: = 之乾。藉此，所製得之薄膜，其特性極適用、乍為電薄膜記憶體用電極材。【實施方式】 =明之高純度Ru粉末，Na、K等各鹼金屬元素之里為心tppm以下，〜之含量為。其中，不 A1及氧、氮、氫等氣體成分，其純度為99.99%以上，亚以將純度作成為99·999%以上為更佳。將Na、κ等各驗金屬元素之含量中控制為ι〇卿㈣ 8 200538563 元素容易於靶絕緣膜中移動，而化之原因。而被強烈指出其有宝以下之理由，係因鹼金屬成為MOS-LSI界面特性劣性。為抑制如此之界面特性含量中控制為l〇wtppm以下劣化，並須將各驗金屬元素之: = Dry. As a result, the properties of the obtained thin film are extremely suitable, and it is an electrode material for electrical thin film memory. [Embodiment] = Mingzhi high-purity Ru powder, the content of each alkali metal element such as Na and K is less than tppm, and the content of ~ is. Among them, the purity of gas components such as A1 and oxygen, nitrogen, and hydrogen is 99.99% or more, and the purity is preferably 99.999% or more. The reason for controlling the content of each metal test element such as Na and κ to ι〇qing㈣ 8 200538563 is that the element is easy to move in the target insulating film. It is strongly pointed out that the reason is as follows. The reason is that alkali metals are inferior in MOS-LSI interface characteristics. In order to suppress such interface characteristics, the content is controlled to be less than 10 wtppm, and the metal test elements must be adjusted.

本發明之特徵在於，具有可微細化靶之組織、可得到減少成膜時粒子果0 以1〜50wtppm之範圍添加a卜使結晶方位隨機化之作用，藉此之產生數、使膜厚分布均一之其效、< A1被視為不佳之元素而極力使其減低至未滿 IPPmH A1不僅不會對半導體特性有大幅影響，且具有上述ms。相較於其作為雜質之影響，其更具有良：添加7L素之作用。更佳為，將A1含量控制為卿㈣之範圍。 Μ之含量若超過50wtppm，則粒子反而會有增多之傾 :。其係基於A1會變成A1203等異物而存在之考量。因此，需要將A1含量之上限值訂為5〇wtppm。另外’將 Fe、Ni、C〇、r*T· 〇、U等過渡元素之含量總 ―以下’將u、Th等各放射性元素之含量叮為1〇卿沖以下。此係因此等Fe、Ni、c〇、cr、C4 過渡凡素’係成為界面接合部不良原因之纟，u、Th 性元素’由於放射之α線會造成元件軟錯誤，故 έ里以才工制各為l〇wtppm以下為佳。過渡元素，作為半導體機器之雜質，雖不會造成很大 9 200538563 之,7v音，但以控制為總計1 00 wtppm以下為佳。又，氧、氮、氫等氣體成分之總量，以控制為丨000wtppm 以下為佳。此係因該等會影響粒子之產生數之故。高純度Ru粉末，係將純度3Ν (99·9%)以下之Ru原料作為陽極，於酸性或氨水溶液中電解進行精製以製造。酉义，以硝酸、鹽酸之溶液為佳。藉此，可以較低成本製得安定品質之高純度Ru粉末。濺鍍靶，可藉由以如此製造之高純度Ru粉末進行燒結來製得。將如此製造之靶於基板上進行濺鍍，可製得均一性優異、作為界電薄膜記憶體用電極材極優特性之薄膜。實施例其次，根據實施例說明本發明。實施例係為了使發明易於理解者，並不因此而限制本發明。亦即，本發明係包 S基方；本發明技術思想之其他實施例及變形。 (實施例1 ) 將表1所示之純度3N級之Ru粉約2kg，置入利用隔膜之陽極盒。於陰極係使用石墨。電解液，係作成pH2之硝酸酸性，以電流5A電解精製2〇hr。之後，將Ru粉由陽極盒中取出，洗淨乾燥。製得Ru粉之純度，同樣示於表1。Na、K之含量分別為 2wtPpm、〇.5wtppm，A1 之含量為 1〇wtppm。將該Rii粉，使用熱壓法以14〇〇°c進行燒結作成靶。並且，使用該靶進行濺鍍。 200538563 所示’得到成膜時之粒一之膜厚分布的優良結其結果同樣示於表1。如表j 子產生數少、且製得之薄膜具有私果。 (實施例2) “ 7表1所示之純度3N級之Ru粉約2kg，置入利用隔膜之陽極盒。於陰極係使用石墨。電解液，係作成pH2之鹽酸酸性，以電流The invention is characterized in that it has a structure capable of miniaturizing a target, and can reduce the particle size during film formation. Adding αb in a range of 1 to 50 wtppm randomizes the crystal orientation, thereby generating numbers and distributing film thickness. Uniformity, < A1 is regarded as a poor element, and it is strongly reduced to less than IPPmH A1 not only does not significantly affect the semiconductor characteristics, but also has the above ms. Compared with its effect as an impurity, it has a better effect: the effect of adding 7L element. More preferably, the A1 content is controlled to be within a range. If the content of M is more than 50wtppm, the particles will increase. It is based on the consideration that A1 will become a foreign object such as A1203. Therefore, it is necessary to set the upper limit of the A1 content to 50 wtppm. In addition, 'the total content of transition elements such as Fe, Ni, Co, r * T · O, U, etc. is-or less', and the content of each radioactive element such as u and Th is set to 10 or less. Therefore, this system waits for the transition of Fe, Ni, co, cr, and C4 to become the cause of poor interface junctions. The u and th elements will cause soft errors due to the alpha radiation of the element. It is preferable that the work systems are each 10 wtppm or less. The transition element, as an impurity of semiconductor devices, does not cause a large 7v sound, but it is better to control it to a total of 100 wtppm or less. In addition, the total amount of gas components such as oxygen, nitrogen, and hydrogen is preferably controlled to not more than 000 wtppm. This is because these will affect the number of particles generated. High-purity Ru powder is produced by electrolytically refining a Ru raw material with a purity of 3N (99 · 9%) or less in an acidic or ammonia solution. The meaning is preferably a solution of nitric acid and hydrochloric acid. As a result, high-purity Ru powder with stable quality can be produced at a lower cost. The sputtering target can be obtained by sintering the thus-prepared high-purity Ru powder. The target thus manufactured is subjected to sputtering on a substrate, so that a thin film having excellent uniformity and excellent characteristics as an electrode material for a thin-film electrical memory can be obtained. Examples Next, the present invention will be described based on examples. The examples are intended to make the invention easier to understand and do not limit the invention accordingly. That is, the present invention is an S-based party; other embodiments and variations of the technical idea of the present invention. (Example 1) About 2 kg of Ru powder having a purity of 3N as shown in Table 1 was placed in an anode box using a separator. For the cathode system, graphite is used. The electrolytic solution was made into a nitric acid of pH 2 and electrolytically refined at a current of 5 A for 20 hr. After that, the Ru powder was taken out of the anode box, washed and dried. The purity of the obtained Ru powder is also shown in Table 1. The contents of Na and K were 2 wtPpm and 0.5 wtppm, respectively, and the content of A1 was 10 wtppm. This Rii powder was sintered at 1400 ° C using a hot pressing method to make a target. Then, sputtering is performed using this target. The results shown in 200538563 are shown in Table 1. As shown in Table j, the number of produced products is small, and the resulting film has private effects. (Example 2) "7 About 2 kg of Ru powder with a purity of 3N as shown in Table 1 was placed in an anode box using a separator. Graphite was used as the cathode. The electrolyte was made acidic with hydrochloric acid at pH 2 and the current

包机A冤解精製2〇hr。之後，將Ru粉由陽極盒中取出，洗淨乾燥。、製得Ru粉之純度，同樣示於表i。Na、κ之含量分別為4wtPpm、lwtppm，八丨之含量為。㈣卯㈤。、：/ RU粕，使用熱壓法以14 0 0。〇進行燒結作成革巴。並且’使用該革巴進行錢錢。其結果同樣示於表卜如| i所示，與實施例j相同，得到成膜時之粒子產生數少、且製得之薄膜具有均一之膜厚分布的優良結果。 (實施例3) *將表1所示之純度3N級之RU粉約2kg，置入利用隔膜之陽極盒。於陰極係使用石墨。電解液，係使用pH9之氨水溶液，以電流5 A電解精製20hr。之後，將Ru粉由陽極盒中取出，洗淨乾燥。製得Rii粉之純度，同樣示於表1。Na、κ之含量分別為〇.5诃印1)111、〇.1〜卯111，乂之含量為7”卯111。將該1111 粉，使用熱壓法以140CTC進行燒結作成靶。並且，使用該革巴進行賤鑛。 200538563 其結果同樣示於表！。如表”斤示，與實施例】相同，得到成膜時之粒子產生數少、且製得之薄膜具有均一之膜厚分布的優良結果。 (貫施例4 )Charter A unjustified refining 20hrs. After that, the Ru powder was taken out of the anode box, washed and dried. The purity of the obtained Ru powder is also shown in Table i. The contents of Na and κ were 4wtPpm and 1wtppm, respectively. Alas. ： / RU meal, using hot pressing method to 14 0 0. 〇 Sintering was performed to form Geba. And ’use this leather for money. The results are also shown in the table as shown in | i. As in Example j, excellent results were obtained in which the number of particles generated during film formation was small and the obtained film had a uniform film thickness distribution. (Example 3) * Approximately 2 kg of RU powder having a purity of 3N as shown in Table 1 was placed in an anode box using a separator. For the cathode system, graphite is used. The electrolytic solution was electrolytically refined at a current of 5 A using an ammonia aqueous solution of pH 9 for 20 hours. After that, the Ru powder was taken out of the anode box, washed and dried. The purity of the obtained Rii powder is also shown in Table 1. The content of Na and kappa are 0.5 诃 1) 111, 0.1 ~ 卯 111, and the content of 乂 is 7 ”卯 111. The 1111 powder was sintered at 140CTC using the hot pressing method as a target. And, Use this leather for low-grade ore. 200538563 The results are also shown in the table ... As shown in the table, the same as in the example, the number of particles generated during film formation is small, and the obtained film has a uniform film thickness distribution. Excellent results. (Example 4)

將表1所示之純度3N級之Ru粉約2kg，置入利用隔膜之陽極盒。於陰極係使用石墨。電解液，係作成pH2之鹽酸酸性’並添加lmg/L之A%，以電流Μ電解精製 20hr。之後，將Ru粉由陽極盒中取出洗淨乾燥。使用熱壓法以行濺鍍。製得Ru粉之純度，同樣示於表1〇Na、K之含量分別為6wtppm、3wtppm ’ A1之含量為43w⑽以。將該Ru粉， 14〇0 C進行燒結作成革巴。並且，使用該革巴進所示，粒子產生數雖有些許變差，但為可容許其結果同樣示於表1。如表1 些許增加，使製得薄膜之膜厚分布之範圍。 (比較例1 ) 直接將純度3N級之Ri】i < Kll叔進仃熱壓製成靶。與原料相同純度之m ' κ分別為8〇wtppm、4〇wtppm，A1之含量為 mwtppm。使用I緣進行賤鍍的結果，如表ι所示，粒子之產生數多，且製得薄臈之膜厚分布亦差。 (比較例2) 將純度3N級之扒、杜― 十刀進仃EB熔煉，製得純度5N級之Ru錠。由於Ru無法推/雨女進仃壓延加工，故直接將錠切割以製造靶。 12 200538563 衣侍之Ru粉之純度，同樣示於表含別為<〇·〜、<〇〜，：之…About 2 kg of Ru powder having a purity of 3N as shown in Table 1 was placed in an anode box using a separator. For the cathode system, graphite is used. The electrolytic solution was made into acidic hydrochloric acid 'at pH 2 and A% of 1 mg / L was added, and electrolytically refined at a current of 20 hr. After that, the Ru powder was taken out of the anode box, washed, and dried. Sputtering was performed using hot pressing. The purity of the obtained Ru powder was also shown in Table 10. The contents of Na and K were 6 wtppm and 3 wtppm, and the content of A1 was 43 w⑽. This Ru powder was sintered at 1400 C to obtain a derivatized spar. In addition, as shown by this Geba Jin, although the particle generation number is slightly deteriorated, the results are also shown in Table 1 as acceptable. As shown in Table 1, it is slightly increased to make the thickness distribution range of the thin film obtained. (Comparative Example 1) A target of Ri] i < Kll having a purity of 3N was directly pressed into a target. The m ′ κ with the same purity as the raw material was 80 wtppm and 40 wtppm, respectively, and the content of A1 was mwtppm. As a result of the base plating using the I edge, as shown in Table I, the number of particles generated was large, and the thickness distribution of the thin film was also poor. (Comparative Example 2) A 3N-grade squeegee and du-ten knife were smelted into EB to obtain a 5N-grade Ru ingot. Since Ru could not push / pull into the calendering process, the ingot was cut directly to make the target. 12 200538563 The purity of Ru powder for clothing service is also shown in the table. It contains < 〇 · ~, < 〇 ~,:

使用該㈣行誠。 U<(UwtPPmQ 革巴之結晶粒徑粗大化声八士 + 杻子之產生數顯著變多、且膜厚分布亦非常差。由以上所述，了夂夕丑 .了解RU靶為燒結體係佳。 (比較例3 ) έ以與實施例1相同之粉末製造方法，但電解精製時門 ^為^使用如此製得之以粉作絲士之純度為物，之:7:Α1之含量較本發明之基準值為高，亦即，Na、 κ之=分別為伽PPm、15wtppm，A1之含量為心_。接者，使用如此製得之靶進行濺鍍。 Q果如表1所不，侍到粒子產生數變多、且製得薄變差的結果。 u錢之域厚分布亦稍稍 (比較例4) :=施例"目同之粉末製造方法，但電解精製時間曰長為嶋r。使用如此製得之^粉作成乾。乾之純度為 4N，但使用A1含量較本發明之基準值低 .^ 、不兩 1 wtppm) 之Ru粉作成|巴，其他雜質之含量如表丨所示接著，使用如此製得之靶進行濺鍍。苴处 — 一 x、、、'°果如表1所不，粒徑稍微變大、膜厚分布變差、且粒 J要文亦增加。作為把之製造原料之高純度RU粉末中认人p τ，將Na、K等双至屬凡素之含量控制成各為10wtppm以下、u'Th等放射性元素之含量控制成各為1 O b以下、且使其含有A1 5〇PPm ’藉此，可製造乾之結晶粒徑小、成膜時粒子之 13 200538563 產生數少、且膜厚分布均一之靶。藉此，可製得具極優特性之薄膜，而極適用於作為界電薄膜記憶體用電極材。Use that honesty. U < (UwtPPmQ Geba's crystal grain size is coarsened, and the number of sonic bastards + rice dumplings is significantly increased, and the film thickness distribution is also very poor. From the above, we know that the RU target is a good sintering system (Comparative Example 3) The same powder manufacturing method as in Example 1 was used, but the door was electrolytically refined ^ is ^ using the powder made of silk so obtained, the content is: 7: A1 The reference value of the invention is high, that is, Na, κ = gamma PPm, 15wtppm, and the content of A1 is the heart _. Then, the target thus prepared is used for sputtering. Q results are not as shown in Table 1, The result is that the number of particles is increased, and the result is thinner and weaker. UThe thickness distribution of the domain is also slightly (Comparative Example 4): = Example " The same powder manufacturing method, but the electrolytic refining time is as long as嶋 r. Use the ^ powder thus prepared to make it dry. The purity of the dry is 4N, but use Ru powder whose content of A1 is lower than the reference value of the present invention (^, not more than 1 wtppm) to make bar | Other impurities such as As shown in Table 丨, sputtering was performed using the target thus prepared.苴 — — As shown in Table 1, the particle size becomes slightly larger, the film thickness distribution becomes worse, and the grain size increases. As high-purity RU powder used as a raw material for manufacturing, it is recognized that p τ, and the content of bisphenols such as Na and K is controlled to 10 wtppm or less, and the content of radioactive elements such as u'Th is controlled to 1 O b each. In the following, it is made to contain A1 50 PPm ', thereby making it possible to produce a target with a small dry crystal particle size, a small number of particles during film formation, and a uniform film thickness distribution. Thereby, a thin film having excellent characteristics can be obtained, which is extremely suitable as an electrode material for a thin film memory.

14 20053856314 200538563

(mdd) 比較例4 〇 r-H Ο m (N (N cn <N (N T—H 00 o 〇 (N 〇 T-H <N VD 比較例3 〇 uo in m (N m m CN <N t-H o (N t-H m CN 〇比較例2 <0.1 <0.1 <0.1 <0.1 m <0.1 <0.1 <0.1 <10 400 ±15 比較例1 § o 00 m 00 m cn <N CN Τ-Ή o r-H H VO <N 200 o (N 實施例4 cn (N 寸 CN Oj m <N Ο r-H 實施例3 in 〇 t-H o 〇 cn 00 t-H … CN <N ▼-H 卜 m CN 〇寸· m rq 實施例2 寸 (N r—^ CN CN rn T-H in T—1 (N (N § o 寸· 卜 rq 實施例1 d oo (N m rj (N o r—H (N o VO cn ΐ! 原料 g o 00 m 00 cn m rsi (N 1—H o f—H vo (N 200 1 1 • a Z (D Ph m > rH O 革巴平均粒徑(μιη) 粒子量 (個/晶圓）膜厚分布(％) 200538563(mdd) Comparative Example 4 〇rH Ο m (N (N cn < N (NT-H 00 o 〇 (N 〇TH < N VD Comparative Example 3 uoo m (N mm CN < N tH o ( N tH m CN 〇 Comparative Example 2 < 0.1 < 0.1 < 0.1 < 0.1 m < 0.1 < 0.1 < 0.1 < 10 400 ± 15 Comparative Example 1 § o 00 m 00 m cn < N CN Τ-Ή o rH H VO < N 200 o (N Example 4 cn (N inch CN Oj m < N Ο rH Example 3 in 〇tH o 〇cn 00 tH… CN < N ▼ -H mm CN 〇 inch m rq Example 2 inch (N r — ^ CN CN rn TH in T — 1 (N (N § o inch · r rq Example 1 d oo (N m rj (N or —H (N o VO cn ΐ! Raw material go 00 m 00 cn m rsi (N 1—H of—H vo (N 200 1 1 • a Z (D Ph m > rH O Geba average particle size (μιη)) particle size (a / Wafer) Film thickness distribution (%) 200538563

【圖式簡單說明】無【主要元件符號說明】益 16[Brief description of the diagram] None [Description of the main component symbols] Yi 16

Claims

200538563 十、申請專利範圍： 1 · 一種鬲純度Ru粉末’其特徵在於，na、K等驗金屬元素之含量各為lOwtppm以下、A1含量為。 2. —種高純度RU粉末，其特徵在於，A1含量為 5〜20wtppm。 3·如申請專利範圍第1或第2項之高純度粉末，其中，Fe、Ni、Co、Cr、Cu等過渡金屬元素之含量總計為 lOOwtppm以下，且u、Th等放射性元素之含量各為丨〇wtppb Φ以下。 4·如申凊專利範圍第1或第2項之高純度Ru粉末，不計氧、氮、氫等氣體成分，其純度為99.99%以上。 5 ·如申請專利範圍第3項之高純度RU粉末，不計氧、氮、氫等氣體成分，其純度為99.99%以上。 6·如申請專利範圍第4項之高純度RU粉末，其中，氧為lOOwtppm以下〇 _ 7·如申請專利範圍第5項之高純度RU粉末，其中，氧為lOOwtppm以下。 8. —種濺鍍靶，其特徵在於，係由申請專利範圍第第7項中任一項之高純度Ru粉末進行燒結而製成。 9. 一種薄膜，其特徵在於，係由申請專利範圍第1〜第 7項中任一項之高純度Ru粉末燒結成之濺鍍靶進行濺鍍而 1〇·一種高純度Ru粉末之製造方法，項中任一項之高純度專利範圍第1〜第係用來製造申請 Ru粉末，其特徵 17 200538563 在於，以純度3N ( 99.9%)以下之Ru原料作為陽極，於溶液中進行電解而精製。十一、圖式：無200538563 10. Scope of patent application: 1. A rubidium-purity Ru powder 'is characterized in that the content of metal detection elements such as na and K is 10 wtppm or less, and the content of A1 is 2. A high-purity RU powder, characterized in that the A1 content is 5 to 20 wtppm. 3. If the high-purity powder of item 1 or 2 of the scope of patent application, the total content of transition metal elements such as Fe, Ni, Co, Cr, Cu and so on is 100wtppm or less, and the content of radioactive elements such as u and Th is each丨〇wtppb Φ or less. 4. If the high-purity Ru powder in the first or second item of the patent application of Shenyin, excluding oxygen, nitrogen, hydrogen and other gas components, its purity is above 99.99%. 5 · If the high-purity RU powder in item 3 of the patent application scope, excluding oxygen, nitrogen, hydrogen and other gas components, its purity is above 99.99%. 6. The high-purity RU powder according to item 4 of the patent application, wherein oxygen is 100 wtppm or less. _7. The high-purity RU powder according to item 5 of the patent application, wherein oxygen is 100wtppm or less. 8. A sputtering target, characterized in that it is made by sintering a high-purity Ru powder according to any one of item 7 of the scope of patent application. 9. A thin film, characterized in that it is sputtered from a sputtering target obtained by sintering a high-purity Ru powder according to any one of claims 1 to 7, and a method for manufacturing a high-purity Ru powder The high-purity patent scope of any one of the first to the first series is used to manufacture Ru powder for application. The feature 17 200538563 is that the Ru raw material with a purity of 3N (99.9%) or less is used as the anode, and is refined by electrolysis in a solution. . Eleven schemes: None

18 200538563 七、指定代表圖： (一）本案指定代表圖為：第（無）圖。 (二) 本代表圖之元件符號簡單說明：無八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：18 200538563 VII. Designated Representative Map: (1) The designated representative map in this case is: (none) map. (2) Brief description of the component symbols of this representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: